Processing additives for blended cements

ABSTRACT

This invention relates to a method of enhancing the later age strength of certain blended cements. Under the process of this invention, certain blended cements, in particular those made from cement clinkers containing at least 4% C4AF, when mixed with up to 0.2% of a higher trialkanolamine exhibit a marked increase in 7 and 28-day compressive strengths. The blended cements of this invention contain between 5 and 80% fillers or clinker substitutes. The higher trialkanolamine strength enhancing additive may be admixed with the cement powder or may be interground with the cement clinker during finish milling.

This application is a continuation-in-part application of copending U.S. application Ser. No. 4,918,437, filed Oct. 6, 1989, U.S. Pat. No. 4,943,323.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a strength enhanced blended cement, and more specifically to a hydraulic blended cement containing an additive which may be interground with cement clinker to improve grinding efficiency or may be intermixed with the powdered cement prior to or in conjunction with the addition of water and which improves the strength-set time profile of the blended cement to a level substantially equivalent to high quality portland cement.

2. Description of the Prior Art

The term cement is used to designate many different kinds of materials useful as binders or adhesives. Hydraulic cements are powdered materials which, when mixed with water, form a "paste" that hardens slowly. If, further, mixed with sand it forms a "mortar" and if mixed with sand and course aggregate, it forms a "concrete" which are rockhard products. These products are commonly referred to as hydraulic cement mixes. Portland cement is distinguished from other cements by the different components of which it is composed, and the requirement that it meet particular standard specifications established in each country (see Cement Standards of the World, Cembureau, Paris, Fr.) For example, in the United States, the American Society for Testing and Materials (ASTM), American Association of State Highway and Transportation Officials, as well as other government agencies, have set certain basic standards for cement which are based on principal chemical composition requirements of the clinker and principal physical property requirements of the final cement mix. For purposes of this invention the term "portland cement" is intended to include all cementitious compositions which meet the requirements of the ASTM (as designated by ASTM Specification C150).

Portland cement is prepared by sintering a mixture of components including calcium carbonate (as limestone), aluminum silicate (as clay or shale), silicon dioxide (as sand) and miscellaneous iron oxides. During the sintering process, chemical reactions take place wherein hardened nodules, commonly called clinkers, are formed. Portland cement clinker is formed by the reaction of calcium oxide with acidic components to give primarily tricalcium silicate, dicalcium silicate, tricalcium aluminate, and a ferrite solid solution phase approximating tetracalcium aluminoferrite. For purposes of this invention, the variable compositions encompassing the calcium ferrite solid solution will be referred to as tetracalcium aluminoferrite. The conventional cement chemists' notation uses the following abbreviations:

CaO=C

SiO₂ =S

Al₂ O₃ =A

Fe₂ O₃ =F

thus:

tricalcium silicate=C₃ S

dicalcium silicate=C₂ S

trialcium aluminate=C₃ A

tetracalcium aluminoferrite=C₄ AF

After the clinker has cooled, it is then pulverized together with a small amount of gypsum (calcium sulfate) in a finish grinding mill to provide a fine, homogeneous powdery product known as portland cement Due to the extreme hardness of the clinkers, a large amount of energy is required to properly mill them into a suitable powder form. Energy requirements for finish grinding can vary from about 33 to 77 kW h/ton depending upon the nature of the clinker. Several materials such as glycols, alkanolamines, amine acetates, aromatic acetates, etc., have been shown to reduce the amount of energy required and thereby improve the efficiency of the grinding of the hard clinkers. These materials, commonly known as grinding aids, are processing additives which are introduced into the mill in small dosages and interground with the clinker to attain a uniform powdery mixture. In addition to reducing grinding energy, the commonly used processing additives listed above are frequently used to improve the ability of the powder to flow easily and reduce its tendency to form lumps during storage.

Because of the rigid compositional and physical requirements for forming suitable portland cement clinker, clinker becomes a relatively expensive raw material. For certain applications, it is possible to substitute less expensive fillers such as limestone or clinker substitutes such as granulated blast furnace slags, natural or artificial pozzolana, and the like, for a portion of the clinker. As used herein, the term filler refers to an inert material that has no later age strength enhancing attributes; the term "clinker substitute" refers to a material that may contribute to long term compressive strength enhancement, but usually exhibits little or no enhancement of 7 or 28-day compressive strength values. The addition of these fillers or clinker substitutes to form "Blended Cements" is limited in practice by the fact that such addition usually results in a diminution in the physical strength properties of the resultant cement. For example, when a filler such as limestone is blended in amounts greater than 5%, the resultant cement exhibits a marked reduction in strength, particularly with respect to the strength attained after 28 days of moist curing (28-day strength). The 28-day strength has particular significance and will be emphasized throughout this invention since it is the strength at this age which is most commonly used to assess the engineering properties of the final cement products. As used herein, the term "Blended Cements" refers to hydraulic cement compositions containing between 5 and 80% more conventionally between 5 and 60%, fillers or clinker substitute materials.

Various other additives may be added to cement to alter the physical properties of the final cement. For example, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and the like are known to shorten the set time (set accelerators) as well as enhance the one-day compressive strength (early strength) of cements. However, these additives usually have little beneficial effect on the 28-day set strength of the finished cement and in some cases may actually diminish it. Various other polymeric amines and imines have been used as 28-day cement strength enhancers, however, due to the high costs of these additives, their use is somewhat limited.

It has now been discovered that certain tertiary amines classified as tri(hydroxyalkyl) amines having at least one C₃ -C₅ hydroxyalkyl group (hereinafter referred to as "higher trialkanolamine"), as fully described herein below, surprisingly imparts 7 and 28-day compressive strength enhancing properties to certain hydraulic blended cements. This discovery includes the use of triisopropanolamine (TIPA), which was previously believed to possess the equivalent cement additive properties as triethanolamine (TEA) (i.e., shortening set times and enhancing one-day compressive strengths,) but, instead, surprisingly exhibits unique 7 and 28-day compressive strength enhancing properties when added to certain hydraulic blended cements. Suitable hydraulic blended cements for use in the invention are those made from cement clinkers containing at least 4% tetracalcium aluminoferrite (C₄ AF) by weight. The enhanced 7 and 28-day strength exhibited by these cements were unexpected and unobvious since C₄ AF was believed to have no cementing value. These enhanced blended cement compositions are useful as a portland cement replacement.

SUMMARY OF THE INVENTION

It is an object of this invention to provide a hydraulic blended cement, prepared from a mixture of clinker, gypsum and a high proportion of filler or clinker substitute, together with a strength enhancing additive wherein the blended cement exhibits a 7 and 28-day strength profile in conformance with portland cement minimum standards.

Another object of this invention is to provide a cement additive that is effective as a grinding aid, improves the ability of the ground cement powder to flow easily, reduces the tendency of the cement to form lumps during storage, and enhances the 7 and 28-day strength.

Another object of this invention is to provide a process to enhance the 7 and 28-day strength of blended cements to a level in conformance with portland cement minimum standards.

In accordance with the present invention, there have been provided certain hydraulic blended cements comprising a mixture of clinker, gypsum and from 5 to 80% fillers or clinker substitutes wherein the clinker contains at least 4% C₄ AF, which when mixed with an additive comprising a higher trialkanolamine produces a hydraulic blended cement that exhibits the equivalent physical 7 and 28-day compressive strength properties of portland cement.

Also provided in accordance with this invention is a method of preparing enhanced strength hydraulic blended cements comprising intergrinding a mixture of clinker containing at least 4% C₄ AF, gypsum and between 5% and 80% by weight filler or clinker substitute, together with an additive that is effective as a grinding aid, improves the ability of the ground cement to flow easily, reduces the tendency of the cement to form lumps during storage, and enhances the 7 and 28-day strength, said additive comprising at least one higher trialkanolamine, as fully described herein below.

DETAILED DESCRIPTION

The present invention is directed to an enhanced strength, hydraulic blended cement having a 7 and 28-day compressive strength in conformance with the minimum standards of a portland cement as defined in ASTM C150. These enhanced strength hydraulic blended cements are prepared by incorporating a strength enhancing additive into a suitable, hydraulic blended cement. The strength enhancing additive is comprised of at least one higher trialkanolamine. The term "higher trialkanolamine" shall refer, in the present description and in the appended claims, to tertiary amine compounds which are tri(hydroxyalkyl) amines having at least one C₃ -C₅ hydroxyalkyl (preferably a C₃ -C₄ hydroxyalkyl) group therein. The remaining, if any, hydroxyalkyl groups of the subject tertiary amine can be selected from C₁ -C₂ hydroxyalkyl groups (preferably C₂ hydroxyalkyl). Examples of such compounds include hydroxyethyl di(hydroxypropyl)amine, di(hydroxyethyl) hydroxypropylamine, tri(hydroxypropyl)amine, hydroxyethyl di(hydroxy-n-butyl)amine, tri(2-hydroxybutyl)amine, hydroxybutyl di(hydroxypropyl)amine, and the like. The preferred higher trialkanolamines of this invention are triisopropanolamine (TIPA), N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine (BHEHPA) and tri(2-hydroxybutyl) amine (T2BA). Mixtures of higher trialkanolamines can be used to effect the 7 and 28-day strength of the blended cement.

The subject invention will be further described in terms of (though not limited to) the preferred higher trialkanolamines, (TIPA), (BHEHPA) and/or tri(2-hydroxybutyl)amine (T2BA). The higher trialkanolamines are added to the cement in an amount up to 0.2%, preferably less than 0.1%, and most preferably between 0.005% and 0.03%, based on the weight of the cement. The additive can be in its neat (amine) form or may be in its neutralized form such as an acetate, gluconate, sulfate, nitrate, nitrite, and the like. Further, the additive may be converted into its ester form (e.g. an ester of an organic acid, preferably a lower acid such as an acetate ester), since, upon addition to the high pH of a hydrating cement, it will undergo hydrolysis and revert back to the alcohol.

A particular advantage of this additive is that it may be either interground or intermixed with the cement. As used herein, the terms "interground" and "intermixed" refer to the particular stage of the cement processing in which the TIPA is added. It has been also found that the subject higher trialkanolamines are effective grinding aids, they may be added to the clinker during the finish grinding stage and thus interground tohelphelp reduce the energy requirements and provide a uniform free flowing cement powder with reduced tendency to form lumps during storage. It is also possible to add the subject additive, such as TIPA, as an admixture to powdered cement either prior to, in conjunction with, or after the addition of water when effecting the hydraulic setting of the cement. Further, the additives of this invention may be supplied in a pure concentrated form, or diluted in aqueous or organic solvents, and may also be used in combination with other chemical admixtures, including but not limited to: accelerating admixtures, air entrainers, air detrainers, water-reducing admixtures, retarding admixtures (as defined in ASTM C494) and the like, and mixtures thereof.

Suitable blended cements for use in this invention are those made from cement clinkers which contain at least 4% tetracalcium aluminoferrite, (C₄ AF), preferably greater than 5.5% C₄ AF, and most preferably greater than 7% C₄ AF. The effectiveness of the subject higher alkanolamines, such as TIPA, BHEHPA or T2BA and the like relates to the amount of C₄ AF in the clinker. Clinkers with low C₄ AF contents, either due to low total iron or to a preponderance of Fe^(II) at the temperature of solidification of the clinker melt phase, or for any other reason, are less affected by the strength enhancing effects of the subject higher alkanolamines. During C₄ AF hydration, ferric ions are produced in solution as a byproduct. Since ferric ions are extremely insoluble at the high pH found in hydrating cement, they immediately precipitate as an amorphous ferric hydroxide gel. This gel coats the cement grain and tends to retard hydration of the cement as a whole. The higher alkanolamines may serve to complex with the iron at high pH and help to remove this iron-rich coating, thereby improving the strength development of the cement. The table in Example 3 clearly illustrates the variation in strength enhancement at 28 days when TIPA was added to cements varying in C₄ AF concentration.

The current method to determine the concentration of C₄ AF in a cement is by the Bogue calculation, as specified in ASTM C150. This calculation provides an estimate of the concentration of the major phases present in a cement based on an elemental analysis. The values obtained may, however, be inaccurate in many cases because the Bogue calculation does not account for differences that may occur in the thermal processing history of the cement clinker or for the presence of minor components. Because the Bogue calculation assumes the iron is present only in the C₄ AF phase, the calculated values for the C₄ AF concentration will be in excess of the actual value when a significant fraction of the iron in a cement is present in phases other than C₄ AF. For example, in the case of cement "L" (as illustrated in examples 3 and 7), the C₄ AF concentration based on the Bogue calculation is close to the normal concentration levels of the other cements, but it actually contains a low C₄ AF level. This suggests that the iron in this cement is not present in the C₄ AF solid solution as is normally the case (and assumed by the Bogue calculation), but is instead located in other phases.

For purposes of this invention, the concentration of C₄ AF in a cement will be calculated using data derived by x-ray diffraction (XRD) since this method is representative of the actual C₄ AF concentration. Under this method, a cement sample is scanned in the region 30° to 35° 2θ (CuK.sub.α). The heights of the 141 C₄ AF peak [h(C₄ AF)] at 33.8° and the 440 C₃ A peak [h(C₃ A)] at 33.3° are measured and the ratio of the 141 C₄ AF peak height to the 440 C₃ A peak height is determined. This peak height ratio is proportional to the actual C₄ AF/C₃ A concentration ratio. However, the proportionality constant (K) is not known and cannot be measured in an unambiguous way. In order to estimate this constant, the C₄ AF/C₃ A concentration ratio was estimated from Bogue calculated values for these two phases in cements where the Bogue calculation is expected to be accurate. These Bogue-calculated C.sub. 4 AF/C₃ A concentration ratios were then divided by the calculated peak height ratio from XRD to determine the proportionality constant, K. K was computed for 10 cements and found to have a value of 1.39±0.47.

Next, this value of K, the XRD data, and the Bogue elemental analysis was used to compute the actual C₄ AF content for each cement. In order to do this, a mass balance was performed for alumina in the cement. The fact that all of the alumina must appear in the cement as C₃ A, C₄ AF, or as an impurity in the silicate phases can be expressed mathematically as

    A.sup.Total =A.sup.C3A +A.sup.C4AF +δA.sup.Total

where δ is defined to be the fraction of alumina which appears in the silicate phases. This equation can be rearranged to yield

    A.sup.Total (1-δ)=A.sup.C4AF (1+A.sup.C3A /A.sup.C4AF).

The ratio A^(C4AF) /A^(C3A) is related to the ratio [C₄ AF]/[C₃ A] by the stoichiometry of the compounds involved, so that

    A.sup.C4AF /A.sup.C3A =0.556 [C.sub.4 AF]/[C.sub.3 A].

A new constant, K*, can be defined such that

    C.sup.C4AF /A.sup.C3A =K* (h(C.sub.4 AF)/h(C.sub.3 A)),

where K*=0.556 K, K being the constant of proportionality defined above. Defining the peak-height ratio

    h(C.sub.4 AF)/h(C.sub.3 A)=r,

the mass balance can be rewritten

    A.sup.C4AF =A.sup.Total (1-δ)/(1+1/K*r).

When the stoichiometric relationship between C₄ AF and A is employed, this can be written in the final form

    [C.sub.4 AF]=4.77 A.sup.Total (1-δ)/(1+1/K*r).

In general, the value of δ to be used in this equation is not known. However, an estimate of the C₄ AF content can be obtained by assuming that all of the alumina is in the C₃ A and C₄ AF phases, or δ=0. This estimate will give the highest possible value for the C₄ AF concentration threshold. Any value of δ>0 will lower the threshold below that computed for δ=0. Using this value for δ, the value of K cited above, the value for r obtained from the XRD experiments, and the alumina content from the elemental analysis, the C₄ AF concentration can be computed for any cement. The C₄ AF concentration was calculated for several cements, as shown in the column on the right in Table VII in example 7. (Note--The C₄ AF content of three cements (K, L, and O) were also measured using a technique described in Bulletin 166 of the Research and Development Laboratories of the Portland Cement Association. The C₄ AF content measured according to this bulletin agreed well with the C₄ AF concentration values obtained by XRD data in all these cases, whereas the Bogue calculated C₄ AF concentration values were inaccurate in two of the three cements (L and O)).

Using these computed C₄ AF concentrations, it appears that all of the cements in which the subject higher trialkanolamine provided strength enhancement have a C₄ AF concentration greater than 4%, whereas the two cements in which no strength enhancement was obtained have a C₄ AF concentration less than 4%. It is apparent then that a C₄ AF concentration greater than 4%, preferably greater than 5.5% and most preferably greater than 7% is required to provide useful strength enhancement at 7 and 28 days with the present additive.

It has been observed that the addition of the subject higher trialkanolamine to cements, while enhancing the later age strength of the cement, also tends to increase the amount of air entrained in the cement. Analysis of various cement samples revealed an increase in air entrainment in excess of 2% when compared to cements containing no additive. Thus, a preferred embodiment of this invention comprises a stable, homogeneous mixture of the strength enhancing additive and an air detraining agent (ADA) capable of reducing or eliminating the increased air entrainment in the cement.

Various air detraining agents are known to those skilled in the art, and a choice of a particular agent is not critical per se to this invention, provided however that it is compatible with the particular higher trialkanolamine contemplated for use (i.e., non-degrading) and is soluble therein, or can be made soluble therein by the addition of further ingredients. Suitable air detraining agents include, but are not limited to, nonionic surfactants such as phosphates including tributylphosphate, phthalates including diisodecylphthalate, block copolymers including polyoxypropylene-polyoxyethylene-block copolymers, and the like.

The higher trialkanolamine /ADA mixture may be admixed with the cement powder, or is preferably interground with the cement clinker. When intergrinding these additive mixtures with the cement clinker during finish milling, it is important to choose an ADA which is relatively nonvolatile to withstand the heat generated by the mill and thus not evaporate. The most preferred ADAs for use when intergrinding with the cement clinker are nonionic polyoxypropylene- polyoxyethylene block copolymers having a molecular weight of at least 2500.

The ratio of the subject higher trialkanolamine to ADA in the mixture is typically in the range of 1:(0.1-2) based on weight, and is preferably in the range 1:(0.15-0.40). The mixture can be added to cements in amounts to provide a dosage of higher trialkanolamine of up to 0.2 wt. percent, preferably between 0.005 and 0.03% based on the weight of the hydraulic cement.

As stated above, the subject additive can be used with blended cements to improve the 7 and 28 day compressive strengths of the resulting structure. The improved blended cement does not, however, exhibit any improved early strength and, therefore, conventional set accelerators and early strength enhances can be incorporated into the blended cement to further improve the cement compositions properties. As stated previously, it is known to enhance early strength by incorporating lower alkanolamines into the cement. Other agents capable of enhancing early strength include alkali metal salts, such as alkali metal hydroxides, sulfates, chlorides, acetates, formates, carbonates, silicates and the like. The preferred alkali metals are sodium and potassium. The alkali metal salt can be interground with the clinkers or added later including as an admixture just prior to structural formation. The alkali metal salt can be from various sources including kiln dust which is known to be rich in this material. The weight ratio of the subject trialkanolamine to alkali metal salt should be from about 0.002 to 4, preferably from about 0.01 to 1. Although alkali metal salts enhance early strength, they are generally believed to have a negative impact on later (28 day) strength. However, it has been found that a combination of these early strength enhancers with the higher trialkanolamine agents provided a blended cement which exhibits enhanced strength both in early (1 day) and latter (7 and 28 days) stages of cure.

Without further elaboration, it is believed that one skilled in the art, using the preceding detailed description, can utilize the present invention to its fullest extent. The following examples are provided to illustrate the invention, but are not to be construed as limiting the invention in any way except as indicated in the appended claims. All parts and percentages are by weight unless otherwise indicated and additives are expressed as percent active ingredient as solids based on the weight of dry cement (% s/c). Compressive strengths of the cement samples were determined in accordance with ASTM method C109.

The following examples were prepared using commercially available cements and clinkers. The following table (Table A) provides an elemental analysis of the cements and clinker as oxides and the corresponding clinker compound compositional analysis as calculated by the Bogue method (ASTM C150). The sample codes as used in this table will be used throughout the following examples to indicate which cements were used therein.

                                      TABLE A                                      __________________________________________________________________________     Analyses of Cements and Clinkers                                               Elemental Analysis As Oxides, % by Mass                                        Cement                                                                              Na.sub.2 O                                                                         K.sub.2 O                                                                         MgO                                                                               CaO                                                                               Al2O3                                                                              Fe2O3                                                                              SiO2                                                                              TiO2                                                                              P2O5                                                                               SO3                                        __________________________________________________________________________     A    0.08                                                                               0.59                                                                              0.71                                                                              64.51                                                                             4.36                                                                               3.43                                                                               21.40                                                                             0.18                                                                              0.03                                                                               2.85                                       B    0.00                                                                               0.74                                                                              3.29                                                                              65.74                                                                             4.25                                                                               2.74                                                                               21.46                                                                             0.20                                                                              0.04                                                                               0.86                                       C    0.31                                                                               0.40                                                                              1.97                                                                              65.78                                                                             3.86                                                                               3.01                                                                               22.44                                                                             0.24                                                                              0.07                                                                               0.58                                       D    0.28                                                                               0.55                                                                              3.80                                                                              64.50                                                                             4.60                                                                               3.60                                                                               21.60                                                                             0.20                                                                              0.10                                                                               0.61                                       E    0.21                                                                               0.38                                                                              3.55                                                                              63.25                                                                             4.40                                                                               2.91                                                                               21.45                                                                             0.23                                                                              0.07                                                                               2.54                                       F    0.15                                                                               0.63                                                                              0.86                                                                              64.65                                                                             4.22                                                                               3.37                                                                               21.51                                                                             0.18                                                                              0.05                                                                               2.80                                       G    0.12                                                                               0.66                                                                              4.22                                                                              63.77                                                                             4.46                                                                               2.89                                                                               22.24                                                                             0.29                                                                              0.06                                                                               0.33                                       H    0.18                                                                               0.73                                                                              2.06                                                                              65.00                                                                             4.12                                                                               3.32                                                                               22.54                                                                             0.23                                                                              0.10                                                                               1.00                                       I    0.29                                                                               0.54                                                                              0.00                                                                              65.00                                                                             5.00                                                                               3.00                                                                               22.00                                                                             0.00                                                                              0.00                                                                               2.00                                       J    0.37                                                                               0.21                                                                              1.84                                                                              64.56                                                                             5.51                                                                               2.74                                                                               20.93                                                                             0.24                                                                              0.07                                                                               1.98                                       K    0.10                                                                               1.10                                                                              1.72                                                                              64.91                                                                             5.81                                                                               2.60                                                                               21.75                                                                             0.33                                                                              0.05                                                                               1.33                                       L    0.12                                                                               0.22                                                                              1.14                                                                              67.25                                                                             6.12                                                                               2.44                                                                               21.89                                                                             0.26                                                                              0.11                                                                               0.02                                       M    0.04                                                                               0.45                                                                              1.60                                                                              65.48                                                                             4.85                                                                               0.19                                                                               21.73                                                                             0.20                                                                              0.00                                                                               2.97                                       N    0.00                                                                               0.71                                                                              1.13                                                                              65.28                                                                             6.03                                                                               4.28                                                                               20.45                                                                             0.45                                                                              0.00                                                                               1.59                                       O    0.10                                                                               0.38                                                                              0.84                                                                              65.44                                                                             2.92                                                                               4.67                                                                               24.14                                                                             0.44                                                                              0.14                                                                               0.08                                       P    0.00                                                                               0.33                                                                              1.31                                                                              62.08                                                                             6.17                                                                               3.46                                                                               20.53                                                                             0.37                                                                              0.00                                                                               3.67                                       Q    0.45                                                                               0.28                                                                              2.73                                                                              60.95                                                                             3.77                                                                               2.19                                                                               21.59                                                                             0.30                                                                              0.00                                                                               2.55                                       T    0.00                                                                               0.32                                                                              3.03                                                                              58.99                                                                             4.63                                                                               4.70                                                                               19.80                                                                             0.34                                                                              0.00                                                                               2.30                                       R    0.00                                                                               0.64                                                                              2.24                                                                              64.56                                                                             4.65                                                                               2.13                                                                               23.76                                                                             0.22                                                                              0.02                                                                               0.95                                       S    0.23                                                                               0.47                                                                              1.84                                                                              65.31                                                                             5.04                                                                               2.63                                                                               23.18                                                                             0.29                                                                              0.16                                                                               0.46                                                            Clinker Compound Compositions                             Analyses of Cements and                                                                             Cement Compounds, ASTM C150                               Clinkers Elemental Analysis                                                                         Calculation                                               As Oxides, % by Mass              Compd.                                       Cement                                                                               L.O.I.                                                                             SrO                                                                               Mn2O3                                                                              Total                                                                              C3S                                                                               C2S                                                                               C3A                                                                               C4AF                                                                               Totals                                       __________________________________________________________________________     A     1.21                                                                               0.03                                                                              0.04                                                                               99.42                                                                              56.25                                                                             18.92                                                                             6.31                                                                              10.44                                                                              91.91                                        B     0.59                                                                               0.03                                                                              0.05                                                                               99.98                                                                              68.00                                                                             10.23                                                                             7.26                                                                              8.34                                                                               98.83                                        C     0.43                                                                               0.22                                                                              0.09                                                                               99.40                                                                              63.27                                                                             16.60                                                                             5.96                                                                              9.16                                                                               94.99                                        D     0.08                                                                               0.00                                                                              0.00                                                                               99.92                                                                              58.61                                                                             17.71                                                                             6.89                                                                              10.95                                                                              94.17                                        E     0.99                                                                               0.00                                                                              0.00                                                                               99.98                                                                              51.49                                                                             22.65                                                                             7.53                                                                              8.86                                                                               90.53                                        F     1.38                                                                               0.05                                                                              0.05                                                                               99.90                                                                              57.01                                                                             18.66                                                                             6.09                                                                              10.25                                                                              92.02                                        G     0.25                                                                               0.12                                                                              0.08                                                                               99.49                                                                              53.20                                                                             23.63                                                                             7.86                                                                              8.79                                                                               93.48                                        H     0.15                                                                               0.07                                                                              0.06                                                                               99.56                                                                              55.82                                                                             22.51                                                                             6.18                                                                              10.10                                                                              94.61                                        I     0.00                                                                               0.00                                                                              0.00                                                                               97.83                                                                              53.83                                                                             22.46                                                                             8.17                                                                              9.13                                                                               93.60                                        J     1.12                                                                               0.12                                                                              0.04                                                                               99.73                                                                              55.09                                                                             18.45                                                                             10.79                                                                             8.34                                                                               92.66                                        K     0.00                                                                               0.00                                                                              0.00                                                                               99.70                                                                              49.85                                                                             24.75                                                                             12.00                                                                             7.91                                                                               94.52                                        L     0.00                                                                               0.00                                                                              0.00                                                                               99.57                                                                              60.26                                                                             17.29                                                                             13.07                                                                             7.42                                                                               98.05                                        M     2.03                                                                               0.00                                                                              0.00                                                                               99.54                                                                              58.75                                                                             17.98                                                                             13.06                                                                             0.58                                                                               90.37                                        N     0.71                                                                               0.00                                                                              0.00                                                                               100.63                                                                             56.15                                                                             16.27                                                                             9.93                                                                              13.02                                                                              95.37                                        O     0.00                                                                               0.00                                                                              0.00                                                                               99.15                                                                              52.52                                                                             29.59                                                                             1.37                                                                              14.21                                                                              97.69                                        P     1.04                                                                               0.00                                                                              0.00                                                                               99.46                                                                              37.35                                                                             30.68                                                                             11.48                                                                             10.53                                                                              90.04                                        Q     1.92                                                                               0.00                                                                              0.00                                                                               96.73                                                                              46.30                                                                             26.97                                                                             7.08                                                                              6.66                                                                               87.01                                        T     4.04                                                                               0.00                                                                              0.00                                                                               98.15                                                                              43.00                                                                             24.33                                                                             5.22                                                                              14.30                                                                              86.85                                        R     0.44                                                                               0.00                                                                              0.02                                                                               99.63                                                                              43.64                                                                             35.20                                                                             9.35                                                                              6.48                                                                               94.67                                        S     0.00                                                                               0.00                                                                              0.00                                                                               99.61                                                                              47.75                                                                             30.43                                                                             10.10                                                                             8.00                                                                               96.29                                        __________________________________________________________________________

EXAMPLE 1

This example illustrates the enhanced strength obtained by limestone blended cements (LBC) relative to portland cements (PC) when interground with triisopropanolamine. Three samples of portland cement clinker were obtained and analyzed for C₄ AF content by x-ray diffraction. As indicated in Table I, all three cement clinkers contained greater than 4% C₄ AF. The limestone blended cements were produced by mixing 2500 g of a mixture of clinker, gypsum, and limestone in a laboratory ball mill and grinding the mixture to a fine powder by revolving the mill 4000 times. The resulting cement was used to produce ASTM C109 mortars. The relative strength of limestone blended cement as compared to a portland cement was determined by producing cements with the following compositions:

(1) blank (no limestone or TIPA)

(2) TIPA only

(3) limestone only

(4) limestone and TIPA.

The samples were allowed to cure to an age of 28 days under limewater, and then evaluated for relative strength. The C₄ AF concentrations were determined by x-ray diffraction analysis for each of the cements. Table I below shows a significant 28-day strength enhancement obtained in the limestone blended cements containing 0.02% TIPA as compared to the ordinary portland cement.

                  TABLE I                                                          ______________________________________                                         Strength Enhancement with TIPA                                                 in Limestone Blended Cements                                                                28 Day Strength,                                                               psi                                                                      %                      0.02% Strength                                   Clinker                                                                               C.sub.4 AF                                                                            Cement   Blank  TIPA  Enhancement, %                             ______________________________________                                         D      9.99   PC       6850   7460   +9                                                      LBC      4200   4900  +17                                        H      8.38   PC       6630   7990  +21                                                      LBC      4020   4970  +24                                        C      8.83   PC       6940   7570   +9                                                      LBC      5230   6470  +24                                        ______________________________________                                          Note:                                                                          PC = Portland Cement (95% clinker, 5% gypsum)                                  LBC = Limestone Blended Cement (75% clinker, 20% limestone, 5% gypsum)   

EXAMPLE 2

This example illustrates the unexpected superiority of TIPA as a 7 and 28-day strength enhancer when compared to triethanolamine (TEA).

A number of limestone blended cements were produced by combining 2500 g of a mixture of clinker, gypsum, limestone, and the desired processing additive in a laboratory ball mill, and grinding the materials to a fine powder by revolving the mill 4000 times. Unless otherwise noted, the composition of each cement was 1875 g clinker, 500 g limestone, and 125 g gypsum. Standard mortars were produced with these cements using the procedure specified in ASTM C109 (w/c=0.485, sand/cement=2.75), and compressive strengths of 2 inch cubes made with the mortars measured at 1, 7 and 28 days. For each clinker used, at least two cements were produced: one with no addition of processing additive, and one in which 0.5 g of TIPA was added to the 2500 g batch of cement (a 0.02% addition) after the initial 100 revolutions of the mill. In some cases a third cement was produced in which 0.5 g of TEA was substituted for TIPA. Table II below shows that for each clinker used, the 28 day compressive strength of the cements containing TIPA exceeded that of the control and, where applicable, the cements containing TEA, except for cement L, which has a C₄ AF content less than 4%. At 7 days, TIPA outperformed the control and TEA for all but cements L and O.

                  TABLE IIa                                                        ______________________________________                                         Results of 1 Day Strength Tests with                                           Laboratory Ground Portland Cements                                                    Compressive Strength at 1 Day, psi.sup.1                                Clinker  Control       TIPA     TEA                                            ______________________________________                                         C        1630(100)     1460(90) 1900(117)                                      C        1610(100)     1550(96) 1810(112)                                      C        1640(100)     1870(114)                                                                               2180(133)                                      C        1740(100)     2080(120)                                                                               2240(129)                                      C        1660(100)     2190(132)                                                                               .sup. nm.sup.2                                 D        1270(100)     1520(120)                                                                               nm                                             H        1390(100)     2470(178)                                                                               nm                                             K        2790(100)     3200(115)                                                                               3240(116)                                      K        2230(100)     2490(112)                                                                               2470(111)                                      O         820(100)      840(102)                                                                               1180(144)                                      O         830(100)      990(119)                                                                               1210(146)                                      L        2020(100)     1630(81) 1850(92)                                       L         660(100)      290(44)  460(70)                                       G        2220(100)     2260(102)                                                                               nm                                             B        1880(100)     2260(120)                                                                               2280(121)                                      ______________________________________                                    

                  TABLE IIb                                                        ______________________________________                                         Results of 1 Day Strength Tests with                                           Laboratory Ground Portland Cements                                                    Compressive Strength at 1 Day, psi.sup.1                                Clinker  Control       TIPA     TEA                                            ______________________________________                                         C        4420(100)     4680(106)                                                                               4520(102)                                      C        4150(100)     4840(117)                                                                               4610(111)                                      C        5040(100)     6360(126)                                                                               6120(121)                                      C        5250(100)     6270(119)                                                                               5480(104)                                      C        5170(100)     6280(121)                                                                                nm.sup.2                                      D        4740(100)     5840(123)                                                                               nm                                             H        4750(100)     6020(127)                                                                               nm                                             K        6150(100)     6650(108)                                                                               6030(98)                                       K        5230(100)     6390(122)                                                                               5950(114)                                      O        3980(100)     3850(97) 4540(114)                                      O        3990(100)     4220(106)                                                                               4240(106)                                      L        6010(100)     5640(94) 4960(83)                                       L        4980(100)     4370(88) 4220(85)                                       G        5690(100)     6160(108)                                                                               nm                                             B        6280(100)     7020(112)                                                                               6190(99)                                       ______________________________________                                    

                  TABLE IIc                                                        ______________________________________                                         Results of 28 Day Strength Tests with                                          Laboratory Ground Portland Cements                                                    Compressive Strength at 28 Days, psi.sup.1                              Clinker  Control       TIPA     TEA                                            ______________________________________                                         C        5860(100)     6760(115)                                                                               5640(96)                                       C        6050(100)     7090(117)                                                                               6260(105)                                      C        7350(100)     8010(109)                                                                               7720(105)                                      C        7310(100)     7420(102)                                                                               6800(93)                                       C        7240(100)     8100(112)                                                                               .sup. nm.sup.2                                 D        6850(100)     7460(109)                                                                               nm                                             H        6630(100)     7990(121)                                                                               nm                                             K        7610(100)     8120(107)                                                                               7170(94)                                       K        7370(100)     7850(107)                                                                               7260(99)                                       O        6080(100)     6630(109)                                                                               6890(104)                                      O        6630(100)     6820(103)                                                                               6300(95)                                       L        7300(100)     6520(89) 6340(87)                                       L        6610(100)     5530(84) 5160(78)                                       G        7030(100)     7680(109)                                                                               nm                                             B        7860(100)     8140(104)                                                                               7590(97)                                       ______________________________________                                          .sup.1 values in the parentheses are compressive strengths reported as a       percentage of the control.                                                     .sup.2 nm = not measured                                                 

EXAMPLE 3

A number of portland cements were produced to show the relationship of strength enhancement due to TIPA and the C₄ AF content of the cement. The cement compositions were in the range 95-97% clinker and 3-5% gypsum. A total of 2500 g of cement was produced from these raw materials by revolving the mill 4000 times at 110° C.

Standard mortars were produced with the cements using the procedure specified in ASTM C109 (w/c=0.485, sand/cement=2.75), with compressive strengths of 2-inch cubes made with the mortars measured at 28 days. For each clinker used, at least two cements were produced: one with no addition of any additive, and an identical one in which 0.5 g of TIPA was added to the 2500 g batch of cement (a 0.02% addition) after the initial 100 revolutions of the mill. In some cases a third cement was produced in the same way, but with 0.5 g of TEA added instead of TIPA.

In addition to the mortar tests, the C₄ AF concentration was determined by x-ray diffraction (XRD) analysis for each of the cements. Table III illustrates the relative 28-day compressive strengths of cements containing TIPA as compared to controls (cements containing no additives) and cements containing TEA. In all cases the strength of the cement containing TIPA exceeds that of the control, except in those cements where the C₄ AF concentration is below 4%. This shows that the addition of TIPA is only beneficial for improving the strength of cements containing at least 4% C₄ AF.

                  TABLE III                                                        ______________________________________                                         Results of Strength Tests and X-ray Analyses of                                Laboratory Ground Portland Cements                                             Compressive Strength at 28                                                     Days, psi (% of control)                                                                               C.sub.4 AF                                             Clinker Control  TIPA      TEA    Concentration                                ______________________________________                                         C       5860(100)                                                                               6760(115) 5640(96)                                                                              8.83                                         C       6050(100)                                                                               7090(117) 6360(105)                                                                             8.83                                         C       7350(100)                                                                               8010(109) 7720(105)                                                                             8.83                                         C       7310(100)                                                                               7420(102) 6800(93)                                                                              8.83                                         C       7240(100)                                                                               8100(112) .sup. nm.sup.1                                                                        8.83                                         D       6850(100)                                                                               7460(109) nm     9.99                                         H       6630(100)                                                                               7990(121) nm     8.38                                         K       7610(100)                                                                               8120(107) 7170(94)                                                                              7.16                                         K       7370(100)                                                                               7850(107) 7260(99)                                                                              7.16                                         O       6080(100)                                                                               6630(109) 6890(104)                                                                             7.22                                         O       6630(100)                                                                               6820(103) 6300(95)                                                                              7.22                                         L       7300(100)                                                                               6520(89)  6340(87)                                                                              3.57                                         L       6610(100)                                                                               5530(84)  5160(78)                                                                              3.57                                         G       7030(100)                                                                               7680(109) nm     9.13                                         B       7860(100)                                                                               8140(104) 7590(97)                                                                              9.97                                         ______________________________________                                          .sup.1 not measured                                                      

EXAMPLE 4

This example illustrates the effectiveness of TIPA as a strength enhancer when used as an admixture in cement powders. Two-inch mortar cubes were produced from a number of commercially available cements using the procedure specified in ASTM C109. Additives, if used, were added to the mixing water before addition to the cement. The TIPA dosage was varied in order to determine the optimum rate of addition. Compressive strength measurements at 1, 7, and 28 days show that TIPA enhances the strength of cements when admixed, as well as when interground with cements. The results also show an optimal TIPA dosage in the region of 0.01% to 0.02%; dosages above this level show no further benefit, and in some cases may be detrimental. The data are summarized in Table IV.

                  TABLE IV                                                         ______________________________________                                         Compressive Strengths of ASTM C109 Mortars                                     with Varying TIPA Dosages                                                      TIPA Dosage,   Set time Compressive Strength, psi                              Cement % s/c       hrs.sup.2                                                                               1 Day 7 Days                                                                               28 Days                                ______________________________________                                         A      0.0         3.2      3470  8030  9040                                   A      0.005       3.3      3670  8360  9280                                   A      0.01        3.1      3980  9060  10730                                  A      0.02        3.3      3790  8640  10730                                  A      0.03        3.2      4160  8410  10530                                  A      0.05        3.0      4100  8190  11020                                  A      0.07        3.3      3890  8930  10560                                  A      0.10        3.6      3880  8490  10050                                  P      0.0         nm       nm    3740  5100                                   P      0.005       nm       nm    4150  5100                                   P      0.01        4.1      nm    4420  5450                                   P      0.02        4.0      nm    4330  5360                                   P      0.03        4.3      nm    4430  5160                                   P      0.04        4.1      nm    4350  5440                                   Q      0.0         5.1      1650  4600  6650                                   Q      0.005       5.3      1700  4910  6940                                   Q      0.01        5.5      1730  5230  7460                                   Q      0.02        5.8      1720  5180  7660                                   ______________________________________                                          .sup.1 Test conditions were modified slightly for the experiments with         Cement A; w/c = 0.385 (not 0.485), sand/cement = 2.5 (not 2.75).               .sup.2 Measured with RMU Automatic Recording Penetrometers.              

EXAMPLE 5

The results presented in examples 2 and 3 show that TIPA is generally superior to TEA in its ability to improve the 28 day strength of cements. However, a potential shortcoming of TIPA is its inability to improve the 1-day strength of cements. Since TEA is known to be a good 1-day strength enhancer but not a 28-day strength enhancer, one would expect that replacing a portion of the TIPA with TEA would improve performance of the additive at 1 day, with a corresponding decrease in 28-day strength.

In order to test this, a number of cements were produced in a laboratory-scale ball mill using clinker "C". In the first test portland cement compositions comprising 95% clinker and 5% gypsum were produced Additives were dissolved in 10 ml of deionized water and added to the other materials in the mill after the initial 100 revolutions of the mill. A total of 4000 revolutions were used to grind each cement. Two-inch mortar cubes were produced from these cements according to the method specified in ASTM C109. The mortar cubes were tested for compressive strength at 1, 7 and 28 days. The data in Table V show that replacement of TIPA with TEA improves the 1-day strength, with the 1-day strengths of TIPA/TEA mixtures falling in between those of neat TIPA and neat TEA, as expected. Unexpectedly, however, the replacement of a fraction of the TIPA with TEA also had a positive impact on the 28-day strength. Although the 7 and 28-day strengths of the cement containing neat TEA were far below those of the cements containing neat TIPA, (and in fact was considerably below the blank at 28 days), replacing some of the TIPA with TEA improved the 7-day strengths, and at 28 days the mixed additive performed significantly better than either TEA or TIPA alone.

                  TABLE V                                                          ______________________________________                                         Results of Laboratory Test Grinds with TIPA/TEA Mixtures                                               Compressive Strength,                                          Dosage,                                                                               Set time,                                                                               psi                                                    Additive  % s/c    hrs.sup.1                                                                               1 Day 7 Days                                                                               28 Days                                ______________________________________                                         none      --       5.43     1740  5250  7310                                   TIPA      0.02     5.27     2080  6270  7420                                   TEA       0.02     4.65     2240  5480  6800                                   TIPA:TEA 1:3                                                                             0.02     4.83     2220  5430  8070                                   TIPA:TEA 1:1                                                                             0.02     4.65     2140  6120  7680                                   TIPA:TEA 3:1                                                                             0.02     4.82     2060  6360  8080                                   ______________________________________                                          .sup.1 Measured with RMU Automatic Recording Penetrometers.              

EXAMPLE 6

Several cement samples were produced by mixing varying amounts of clinker, limestone, gypsum, and organic additives in a ball mill and grinding the mixture to a fine powder. A total of 4000 revolutions were used to grind each cement. Two-inch mortar cubes were produced from these cements according to the method specified in ASTM C109. The compressive strengths of these cubes were measured at 1, 7 and 28 days, and the results are summarized in Table VI. As is evident from the data, the substitution of limestone for 10% of the clinker (blank #2) reduced the relative 28 day strength (blank #1). The addition of diethanolamine (DEA) or triethanolamine (TEA) did not compensate the loss of strength due to the reduced clinker content. The addition of tetra(hydroxyethyl) ethylenediamine (THEED), tetra(hydroxypropyl) ethylenediamine (THPED) and triisopropanolamine produced mortars having 28-day compressive strengths in excess of the blank #1 value, with the greatest strength enhancement being produced by TIPA.

Sodium gluconate was added to a cement sample at a dosage of 0.01% together with 0.02% TIPA to test for improvement in early (1-day) and later (7 and 28-day) strengths. This sample showed substantial improvement in 1-day strength along with a small improvement in 28-day strength.

The addition of 0.02% TIPA to the 10% limestone blended cement boosts its strength to a level in excess of that achieved with the pure portland cement. For cements with a sufficient quantity of C₄ AF (greater than 4%), then, the addition of TIPA makes it possible to produce low cost limestone blended cements with properties similar to those of a more expensive portland cement.

                                      TABLE VI                                     __________________________________________________________________________     Results of Tests with Limestone Blended Cements (w/c = 0.485, sand/cement      = 2.75)                                                                        Cement Composition                   Compressive                               (% by Mass)                 Dose                                                                               Set Time                                                                            Strength (psi)                            Clinker                                                                             Clinker                                                                             Limestone                                                                            Gypsum                                                                              Additive                                                                              (% s/s)                                                                            (hrs)                                                                               1 Day                                                                              7 Days                                                                             28 Days                           __________________________________________________________________________     H    95    0    5    Blank #1                                                                              --  4.50 1760                                                                               4120                                                                               5360                              H    85   10    5    Blank #2                                                                              --  3.75 1740                                                                               3920                                                                               5010                              H    85   10    5    DEA    0.02                                                                               4.08 1810                                                                               4030                                                                               4950                              H    85   10    5    TEA    0.02                                                                               3.42 2170                                                                               4250                                                                               5020                              H    85   10    5    THEED  0.02                                                                               3.75 2050                                                                               4310                                                                               5570                              H    85   10    5    THPED  0.02                                                                               3.83 1740                                                                               4400                                                                               6120                              H    85   10    5    TIPA + 0.02                                                                               3.83 2020                                                                               4710                                                                               6580                                                   Na Gluconate                                                                          0.01                                               H    85   10    5    TIPA   0.02                                                                               3.67 1850                                                                               5240                                                                               6500                              D    95    0    5    Blank #1                                                                              --  4.50 1340                                                                               3610                                                                               4760                              D    85   10    5    Blank #2                                                                              --  4.42 1360                                                                               3520                                                                               4690                              D    85   10    5    THEED  0.02                                                                               4.25 2000                                                                               4480                                                                               5580                              D    85   10    5    TIPA   0.02                                                                               4.17 1900                                                                               4620                                                                               6010                              __________________________________________________________________________

EXAMPLE 7 Calculation of the lowest C₄ AF content with which TIPA will be useful as a strength enhancer.

In the specification it was explained that the C₄ AF content computed by the Bogue calculation is often in error, particularly in cases where time-temperature history of the clinker melt phase allows large quantities of iron to remain in the silicate phases of the hardened product. In the following table, cement "L" is one such example. In this case, the Bogue calculation predicts a large quantity of crystalline C₄ AF to be present, while the XRD pattern shows that very little is actually there. Since the strength enhancing properties of TIPA depend upon the presence of C₄ AF, it was not surprising that TIPA was ineffective with this cement. There must, then be a C₄ AF content threshold below which TIPA is not useful. Based on the strength enhancement data and the Bogue-calculated C₄ AF contents in Table VII, the threshold would appear to be somewhere above 7.4%. However, since the XRD data show that the Bogue calculation overestimates the C₄ AF content for cement "L", the threshold is actually considerably less than this value. In order to better define the C₄ AF threshold concentration, a combination of the XRD and the elemental analysis of the cements cited in prior examples was used to determine actual C₄ AF contents, as outlined in the specification The data in Table VII shows that at least 4% C₄ AF must be present in the cement in order to achieve 28-day strength enhancement with TIPA.

                  TABLE VII                                                        ______________________________________                                         Correlation Between Strength Enhancement with TIPA and the                     Computed C.sub.4 AF Concentration for 12 Cements                                         [C.sub.4 AF]  28 Day Strength                                                                From      of Cement with                               Cement/                                                                               Type of  From    calculation                                                                              TIPA,                                        Clinker                                                                               Addition.sup.1                                                                          Bogue   derived in text                                                                          % of Control                                 ______________________________________                                         E      Ad       8.855   9.263     123                                          H      I.G.     10.103  8.381     121                                          I      Ad       9.129   8.384     119                                          I      Ad       9.129   8.384     119                                          C      I.G.     9.159   8.831     117                                          C      I.G.     9.159   8.831     115                                          F      Ad       10.255  8.686     115                                          C      I.G.     9.159   8.831     112                                          J      Ad       8.338   7.649     109                                          C      I.G.     9.159   8.831     109                                          G      I.G.     8.794   9.126     109                                          D      I.G.     10.955  9.994     109                                          K      I.G.     7.912   7.162     107                                          K      I.G.     7.912   7.162     107                                          B      I.G.     8.338   9.972     104                                          O      I.G.     14.211  7.221     103                                          C      I.G.     9.159   8.831     102                                          M      Ad       0.578   1.350      91                                          L      I.G.     7.425   3.572      89                                          L      I.G.     7.425   3.572      84                                          ______________________________________                                          .sup.1 "Ad" = admixed, "I.G." - interground                              

EXAMPLE 8

Masonry cements are a special subset of the class of limestone blended cements, usually containing 45% to 60% limestone by weight. Masonry cements were produced by grinding clinker, gypsum, and limestone, in the proportions listed in Table VIII, for 5600 revolutions of a laboratory ball mill. Besides these inorganic ingredients, a triethanolamine acetate grinding aid was added to each of the cements at a dosage of 0.02% to insure that an appropriate level of cement fineness was achieved. In two cases, TIPA was also added at the 0.02% dosage. Two-inch mortar cubes were prepared from these cements, using a mortar consisting of 980 g cement, 1680 g ASTM C109 graded sand, 1680 g ASTM C185 20-30 sand, and water corresponding to the water/cement ratio listed in the table. The cubes were cured and strength testing performed following the procedure in ASTM C109. The results shown in Table VIII indicate that TIPA is an excellent 7 and 28-day strength enhancer for masonry cements containing between 45 and 60% limestone.

                                      TABLE VIII                                   __________________________________________________________________________     Results of Test Grinds with Masonry Cements                                                                 Mortar Compressive                                Composition            Mortar                                                                               Strength, psi                                     Clinker                                                                             Limestone                                                                            Gypsum                                                                              Additive.sup.1                                                                        w/c ratio.sup.2                                                                      1 Day                                                                              7 Days                                                                             28 Days                                   __________________________________________________________________________     47.5 50    2.5  none   0.56  890 2050                                                                               2510                                      47.5 50    2.5  0.02% TIPA                                                                            0.53  780 2200                                                                               2780                                      50.0 50    0.0  none   0.54  630 1930                                                                               2390                                      50.0 50    0.0  0.02% TIPA                                                                            0.54  630 2150                                                                               2790                                      __________________________________________________________________________      .sup.1 Triethanolamine acetate was added to each cement at a 0.02% dosage      .sup.2 "w/c" = water/cement ratio. This ratio was adjusted to obtain an        initial mortar flow (as defined in ASTM C109) of 110 ± 5%.            

EXAMPLE 9

Cements were produced by grinding a mixture of clinker (N) (79.3%), limestone (14.9%), kiln dust (2.9%), and gypsum (2.9%) for 2500 revolutions of a laboratory scale ball mill. TIPA (0.5 g in 2500 g of cement, or 0.02%) was added to each cement after 100 revolutions of the mill. In all but one case, an air detraining agent was also added at this stage. Mortar cubes were produced for compressive strength tests using the procedure specified in ASTM C109, and standard mortars for air content tests were produced according to ASTM C185. The results of these tests are shown in Table IX. Note that all of the tested air detraining agents were effective in lowering the air content relative to the control which only contained TIPA. The addition of the air detrainers also had the effect of improving the compressive strengths at all ages.

                  TABLE IX                                                         ______________________________________                                         TIPA/Air Detraining Agent (ADA) Mixtures                                                                       Compressive                                                                    Strength,                                             ADA   Blaine  ASTM C-185 psi                                                     Dose    SSA,    Air      1    7    28                                 ADA      % s/c   %       Content, %                                                                              Day  Days Days                               ______________________________________                                         none     --      401     9.2      2210 4430 4920                               Co-Polymer.sup.1                                                                        0.004   392     8.1      2650 5150 5530                               Co-Polymer                                                                              0.005   407     7.9      2670 4960 5200                               DF110L.sup.2                                                                            0.005   404     8.1      2480 4540 5080                               Motor Oil.sup.3                                                                         0.005   399     8.3      2490 4560 5320                               DIDP.sup.4                                                                              0.005   409     8.2      2570 4820 5690                               ______________________________________                                          Notes:                                                                         .sup.1 Co-Polymer is polyoxyethylenepolyoxypropylene block copolymer           having a molecular weight of at least 2500.                                    .sup.2 DF110L is a product of Air Products                                     .sup.3 Motor oil used was 10W30 commercially available from Quaker State.      .sup.4 DIDP = Diisodecylphthalate                                        

EXAMPLE 10

Four tests were conducted using combinations of TIPA and an alkali salt, Na₂ SO₄, with the results summarized in Table X. In the first of these, test 1, the additives were interground with the cement in a laboratory ball mill as described in Example 2. In the remaining tests (2-4) the additives were dissolved in the water used to prepare standard ASTM C109 mortars. The results show that the 28-day strength of the TIPA/Na₂ SO₄ combination was above that of the mix with only NA₂ SO₄ in each case. Also, the 1-day strengths of the mixes with TIPA and NA₂ SO₄ were always above those mixes containing only TIPA. Thus, combinations of TIPA and Na₂ SO₄ provide improved performance over a range of ages, relative to the use of the compounds individually.

                  TABLE X                                                          ______________________________________                                                              Compressive                                                                    Strength,                                                                      psi                                                            Ce-                       1    7    28                                    Test ment   Additives          Day  Days Days                                  ______________________________________                                         1    O      none                520 4110 6210                                       O      0.02% TIPA          580 3740 6800                                       O      1.0% Na.sub.2 SO.sub.4                                                                             520 3810 5230                                       O      0.2% TIPA + 1.0% Na.sub.2 SO.sub.4                                                                 660 4570 6720                                  2    T      none               1220 4530 6320                                       T      0.02% TIPA         1320 5060 7160                                       T      1.0% Na.sub.2 SO.sub.4                                                                            1760 4120 5030                                       T      0.02% TIPA + 2.0% Na.sub.2 SO.sub.4                                                               1800 4960 6390                                  3    Q      none               1290 3780 6010                                       Q      0.02% TIPA         1420 4210 7070                                       Q      0.02% NaSo.sub.4   1410 4010 6120                                       Q      0.02% TIPA + 0.02% Na.sub.2 SO.sub.4                                                              1440 4250 6910                                       Q      0.02 TIPA + 0.04% NaSO.sub.4                                                                      1530 4280 6820                                  4    T      none               1300 4110 6120                                       T      0.02% TIPA         1510 4610 6740                                       T      0.02% TIPA + 0.02% Na.sub.2 SO.sub.4                                                              1610 4800 6830                                       T      0.02% TIPA + 0.10% Na.sub.2 SO.sub.4                                                              1810 5000 6940                                       T      0.02% TIPA + 0.50% Na.sub.2 SO.sub.4                                                              2020 4850 6520                                  ______________________________________                                          Note:                                                                          In test 1 the ingredients were interground with the cement. In the             remaining tests the additives were admixed.                              

EXAMPLE 11

Example II contrasts performance of TIPA from that of TEA; specifically, TIPA is far superior as a 7- and 28-day strength enhancer. Another higher molecular weight trihydroxyalkylamine, N,N-bis(2-hydroxyethyl)2-hydroxypropylamine (BHEHPA) was used and compared with TEA in the same manner as Example 2 except that the additives were admixed with the cement by predissolving them in the mix water used to prepare standard ASTM C109 mortars. Results are shown in Table XI. The substantial improvement in the 28-day strength shown when this additive was admixed with cement F indicates that this compound has later-age strength-enhancing properties similar to TIPA, while being distinctly different from TEA.

                  TABLE XI                                                         ______________________________________                                         Flow         Set Time,                                                                               Compressive Strength, psi                                Additive                                                                               %        hrs      1 Day  7 Days                                                                               28 Days                                 ______________________________________                                         none    104      4.13     1830   4380  5720                                    TEA     111      3.58     1860   4060  5400                                    BHEHPA  108      3.67     1900   4470  6350                                    TIPA    117      nm       2190   4820  6590                                    ______________________________________                                    

EXAMPLE 12

The higher trihydroxyalkylamine, tris(2hydroxybutyl)amine (T2BA), was produced by reacting 1 mole of ammonia (in the form of an aqueous ammonium hydroxide solution) with 3 moles of 1,2-epoxybutane. NMR spectroscopy was used to confirm that the desired chemical product had been obtained. This product was then interground with clinkers R and S using the procedure in Example 2, with the results of mortar tests conducted with these cements shown in Table XII. Note that at the 0.02% dosage, T2BA is an excellent 7 and 28-day strength enhancer. At the 0.01% dosage with clinker R, good strength enhancement was observed at 7 days. At this dosage, however, the 28-day strength was neither improved or adversely affected, showing that the threshold dosage for 28-day strength enhancement by T2BA was not reached. The threshold dosage, which will vary from cement to cement, can be readily determined for any particular cement.

                  TABLE XII                                                        ______________________________________                                                               Compressive                                                                    Strength, psi                                                              Flow     Set time,                                                                             1    7    28                                 Clinker                                                                               Additive   %        hrs    Day  Days Days                               ______________________________________                                         R      none       132      4.78   1140 4290 6990                               R      0.01% T2BA 133      4.50   1300 4560 6950                               R      0.02% T2BA 134      4.53   1340 4750 7420                               S      none       130      5.38   1840 6150 7610                               S      0.02% T2BA 152      5.17   2140 6430 8450                               ______________________________________                                     

What is claimed:
 1. A strength enhanced blended cement comprising a mixture of clinker having at least 4% C₄ AF, gypsum, 5% to 80% by weight filler or clinker substitute together with an effective amount of a strength enhancing additive to increase the 7 and 28-day strength, wherein the additive comprises a higher trialkanolamine having at least one C₃ -C₅ hydroxyalkyl group.
 2. The strength enhanced blended cement according to claim 1 wherein the effective amount of additive is less than 0.2%.
 3. The strength enhanced blended cement according to claim 1 wherein the effective amount of additive is between 0.005% and 0.03%.
 4. The strength enhanced blended cement according to claim 1 wherein the clinker contains at least 5.5% C₄ AF.
 5. The strength enhanced blended cement according to claim 1 wherein the effective amount of additive is between 0.005% and 0.03% and the clinker contains at least 7% C₄ AF.
 6. The strength enhanced blended cement according to claim 1 wherein the additive comprises a mixture of at least one higher trialkanolamine having at least one C₃ -C₅ hydroxyalkyl group and a water soluble alkali metal salt.
 7. The strength enhanced blended cement according to claim 6 wherein the salt is selected from hydroxide, sulfate, chloride, acetate, formate, carbonate, silicate and mixtures therein.
 8. The strength enhanced blended cement of claim 1, 2, 3, 4, 5, 6, or 7 wherein the higher trialkanolamine is selected from triisopropanolamine, N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, tris(2-hydroxybutyl)amine and mixtures thereof.
 9. A cement additive which enhances the strength of hydraulic blended cements which contain a mixture of 5 to 80% filler or clinker substitute and cement clinker having at least 4% C₄ AF, comprising a solution of at least one higher trialkanolamine having at least one C₃ -C₅ hydroxyalkyl group and other cement admixtures selected from the group of accelerating admixtures, air entrainers, air detrainers, water reducing admixtures and retarding admixtures.
 10. The cement additive of claim 9 wherein the higher trialkanolamine is in its neutralized form or as an ester of an organic acid.
 11. A cement additive according to claim 9 wherein the additive comprises a mixture of triisopropanolamine and a polyoxypropylene-polyoxyethylene block copolymer having a molecular weight of at least
 2500. 12. A cement additive according to claim 9 wherein the additive comprises a mixture of triisopropanolamine and triethanolamine.
 13. The cement additive of claim 9, 10, 11, or 12 wherein the higher trialkanolamine is selected from triisopropanolamine, N-N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine, tris(2-hydroxybutyl)amine and mixtures thereof.
 14. A process for enhancing the strength of hydraulic cement mixes formed from hydraulic blended cement comprising, adding an effective amount of a strength enhancing additive to increase the 7 and 28-day strength of the resultant hydraulic cement mix which contains a mixture of 5 to 80% filler or clinker substitute and cement clinker having at least 4% C₄ AF, wherein the additive comprises at least one higher trialkanolamine.
 15. A process for enhancing the strength of hydraulic blended cements according to claim 14 wherein the effective amount of additive is less than 0.2%.
 16. A process for enhancing the strength of hydraulic blended cements according to claim 15 wherein the effective amount of additive is between 0.005 and 0.03%.
 17. A process according to claim 14 wherein the additive comprises a mixture of at least one higher trialkanolamine and at least one cement additive selected from the group of accelerating admixtures, air entrainers, air detrainers, grinding aids, water reducing admixtures, and retarding admixtures.
 18. A process according to claim 17 wherein the additive comprises a mixture of at least one higher trialkanolamine and a polyoxypropylene-polyoxyethylene block copolymer having a molecular weight of at least
 2500. 19. A process according to claim 17 wherein the additive comprises a mixture of at least one higher trialkanolamine and triethanolamine.
 20. The process of claim 14 wherein the additive is added during the formation of the hydraulic blended cement or during formation of the hydraulic cement mix.
 21. A concrete composition comprising sand, coarse aggregate, water and the blended cement of claim 1, 2, 3, 4, 5, 6 or
 7. 